Organic-inorganic membranes

ABSTRACT

The invention relates to organic/inorganic hybrid polymer blends and hybrid polymer blend membranes that are composed of: one polymer acid halide containing SO 2 X, POX 2  or COX groups (X═F, Cl, Br, I); one elemental or metallic oxide or hydroxide, obtained by the hydrolysis and/or the sol/gel reaction of an elemental and/or organometallic compound during the membrane forming process and/or by subsequently treating the membrane in aqueous acidic, alkaline or neutral electrolytes. The invention further relates to hybrid blends and hybrid blend membranes containing polymers that carry SO 3 H, PO 3 H 2  and/or COOH groups, obtained by aqueous, alkaline or acidic hydrolysis of the polymer acid halides contained in the polymer blend or the polymer blend membrane. The invention also relates to methods for producing the inventive hybrid blends and hybrid blend membranes.

DESCRIPTION OF THE INVENTION

[0001] 1. Subject of the Invention

[0002] The invention relates to organic/inorganic hybrid polymer blends and hybrid polymer blend membranes, that are composed of:

[0003] a polymeric acid halide containing —SO₂X, —POX₂ or —COX groups (X═F, Cl, Br, I)

[0004] an element oxide or element hydroxide or metal oxide or metal hydroxide, obtained by the hydrolysis and/or the sol/gel reaction of an element organic and/or metal organic compound during the membrane formation process and/or by subsequently treating the membrane in aqueous acidic, alkaline or neutral electrolytes.

[0005] The invention farther relates to hybrid blends and hybrid blend membranes containing polymers that carry SO₃H, PO₃H₂ and/or COOH groups, obtained by aqueous, alkaline or acidic hydrolysis of the polymeric acid halides contained in the polymer blend or the polymer blend membrane.

[0006] The invention also relates to methods for producing said hybrid blends and hybrid blend membranes.

[0007] 2. State of the Art and its Disadvantages

[0008] The state of the art regarding acid chloride/inorganic hybrid composites is exposed in the following article:

[0009] Nafion sulfonyl fluoride precursor membranes are preswollen in perfluorohydrophenanthrene and immersed in 3-aminopropyltriethoxysilane. Thereafter excess silane is washed out with EtOH. Hybrids are formed, in which by hydrolysis of silane and by reaction of silanes with SO₂F groups SiO₂ networks partially cross-linked with the polymer are formed in the membrane matrix¹.

[0010] Disadvantage of the described system is, that the sol/gel reaction takes place in a preformed membrane and consequently the content of the inorganic polymer phase formed by hydrolysis, of the polymer composite can not be set at will.

[0011] Also hybrid systems of nonionic polymers and metallic respectively elemental oxides have been described in the literature:

[0012] (e) composites of poly(n-butylmethacrylate) and titanium oxide, made by water vapor hydrolysis of titan alkoxides, which had been added to alcoholic solutions of a poly(n-butylmethacrylate) polymer solution, in the polymer matrix after evaporation of the solvent²

[0013] (f) composite membranes of polyetherimide and nanodispersed Sicilian oxide, made by hydrolysis of TEOS in solutions of polyetherimide Ultem® in NMP by addition of 0.15 M HCl solution. After hydrolysis dense or phase inversed membranes are made from this polymer solution. Compatibility of the inorganic with the organic phase was obtained by extra addition of 3-aminopropyltrimethoxysilane (AS)³.

3. OBJECT OF THE INVENTION

[0014] An object of the invention is to provide composites and composite membranes of polymeric acid halides containing in addition an inorganic element/metal oxide/hydroxide phase, which improves the following membrane properties:

[0015] mechanical stability

[0016] thermal stability

[0017] improved water holding ability even at temperatures of >100° C., which is important in particular for the application in membrane fuel cells in the temperature range of >100° C.

[0018] In the process according to the invention organic precursors of element/metal oxides/hydroxides are brought into the polymer solution (alkoxides/esters, acetylacetonates etc).

[0019] The formation of tie inorganic phase in the ionomer happens after the membrane formation by hydrolysis in acidic, alkaline and/or neutral aqueous environment, whereby optionally at the same time or in another step the polymeric acid halide groups may be hydrolyzed to acid groups.

4. OBJECT SOLVED BY THE INVENTION (DESCRIPTION OF THE INVENTION)

[0020] Surprisingly it has been found, that if zirconium(IV) propylate 70, weight % in 1-propanol, Zr(OCH₂CH₂CH₃)₄ is brought into solutions of PSU sulfochloride in tetrahydrofuran, the zirconium(IV) propylate does not hydrolyze in the polymer solution or form a sparingly soluble complex, but is built into the membrane matrix upon evaporation of the solvent. If the zirconium(IV) propylate solution in propanol would be mixed with a solution of PSU sulfochloride (or PSU sulfonic acid or PSU sulfonic acid salt) in a dipolar aprotic solvent like N-methylpyrrolidinone, zirconium(IV) propylate would immediately hydrolyze or precipitate. Surprisingly it has been found, that the organic Zr compound can be hydrolyzed by successive posttreatment of the membrane in aqueous lye and/or water and/or acid to zirconium dioxide or zirconium oxide hydroxide nanodispersed in the membrane matrix. The inorganic zirconium compound can be detected by EDX in the membrane matrix. Also other organometallic compounds like Ti(acac)₂(OiPr)₂ can be mixed with PSU sulfochloride solutions in ether solvents without hydrolysis in the polymer solution and built into the membrane matrix upon evaporation of the solvent.

[0021] The following composites according to the invention can be made. Composite with

[0022] at least one polymeric acid halide with —SO₂X, —POX₂ or —COX groups, whereby X means F, Cl, Br or I, preferably with an aryl main chain polymer backbone and

[0023] at least one salt, element oxide or element hydroxide or metal oxide or metal hydroxide, obtained by hydrolysis of the following classes of element organic and/or metal organic compounds:

[0024] metal/element alkoxides/esters of Ti, Zr, Sn, Si, B, Al

[0025] metal acetylacetonates, e.g. Ti(acac)₄, Zr(acac)₄

[0026] mixed compounds of metal/element alkoxides and metal acetylacetonates, e.g. Ti(acac)₂(OiPr)₂ etc.

[0027] organic amino compounds of Ti, Zr, Sn, Si, B, Al

[0028] during the membrane formation process and/or by posttreatment of the membrane in aqueous acidic, alkaline or neutral electrolytes. By the same posttreatment step or by another aqueous acidic, alkaline or neutral posttreatment step the acid halide groups can be thereby optionally hydrolyzed to the corresponding acid groups, to obtain ionomer (blend) membranes with an additional nanodisperse distributed inorganic phase.

[0029] The following solvents can be used to prepare the membranes according to the invention: dipolar-aprotic solvents such as N-methylpyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) or sulfolane or ether solvents such as tetrahydrofuran, dioxan, glyme, diglyme, triglyme.

[0030] Due to the inorganic phase nanodisperse distributed in the membrane matrix, brought in according to the invention, the profile of properties of acid halide polymer(blends) or proton conducting ionomer(blends) and ionomer(blend)membranes is strongly changed. The proton conductivity rises, whereas the swelling does not increase correspondingly as usual.

[0031] Depending on the content and the nature of the nanodispersed distributed component the permselectivity of the membranes changes also for nonionic permeating molecules (e.g. gases).

[0032] If the hydrolysis is made in phosphoric acid or if a further posttreatment of the membranes with phosphoric acid is made after the hydrolysis, the corresponding metal or element phosphates or hydrogenphosphates or dihydrogenphosphates are generated, which on their part contribute to the proton conductivity.

5. EXAMPLES

[0033] 5.1 Preparation of Ionomer Blend Membrane TH785

[0034] 0.5 g of PSU sulfochloride with about 1 sulfochloride group per repeating unit are dissolved in 3 g THF. Hereafter 0.5307 g of a 70 weight % solution of zirconium(m) propylate in 1-propanol are added. The solution is degassed and is cast thereafter into a Petri dish. The solvent is evaporated at room temperature overnight. After that the formed membrane is posttreated as follows:

[0035] (1) in 10% NaOH at 80° C. for 24 h

[0036] (2) in 10% sulfuric acid at 80° C. for 24 h

[0037] (3) in water at 85° C. for 16 h

[0038] characterization results: IEC [meq SO₃H/g]: 0.77 swelling [%]: 30.9 R_(sp) ^(H+) (0.5 N HCl) [Ω cm]: 28.9

[0039] 5.2 Preparation of Ionomer Blend Membrane TH782

[0040] 0.5 g of PSU sulfochloride with about 1 sulfochloride group per repeating unit are dissolved in 2.5 g THF. Hereafter 0.8817 g of a 75 weight % solution of titanium (IV) bis(acetylacetonato) diisopropylate in 2-propanol are added. The solution is degassed and is cast thereafter into a Petri dish. The solvent is evaporated at room temperature overnight. After that the formed membrane is posttreated as follows:

[0041] (1) in 10% NaOH at 80° C. for 24 h

[0042] (2) in 10% sulfuric acid at 80° C. for 24 h

[0043] (3) in water at 85° C. for 16 h

[0044] characterization results: IEC [meq SO₃H/g]: 0.81 swelling [%]: 39.4 R_(sp) ^(H+) (0.5 N HCl) [Ω cm]: 12

[0045] 6. Novelty of the Invention

[0046] The new inorganic/organic hybrid ionomer(blend)membranes according to the invention and the methods for producing them have not been described to my knowledge in the literature, neither by own nor by other publications.

[0047] 7. Advantages of the Invention

[0048] The new inorganic/organic hybrid membranes according to the invention show an excellent profile of properties:

[0049] good proton conductivity

[0050] good thermal stability

[0051] good mechanical stability

[0052] limited swelling.

[0053] Some membranes according to the invention show, caused by the inorganic oxide/hydroxide in the membrane matrix, an improved water holding ability especially at T>80° C. It is supposed, that the nanodispersion of the inorganic component in the membrane is the reason behind. By mixing of oxide powders into ionomer membranes, as has been proposed in some publications⁴ already, such a fine distribution of the inorganic component in the membrane matrix as with the method according to the invention can not be reached, where the element—organic/metal organic compounds are hydrolyzed only in the membrane matrix to the oxide or (hydrogen)phosphate. Depending on the specific composition the membranes according to the invention show further advantages:

[0054] reduced methanol permeability

[0055] contribution to proton conductivity, especially at T>80° C.

[0056] changed permselectivity, of both charged and uncharged particles

[0057] the membranes are photochemically active, especially those with nanodispersed titanium dioxide.

[0058] special compositions (with titanium dioxide) show photoluminescence

[0059] 8. Keywords

[0060] aryl main chain polymers

[0061] sol/gel process

[0062] hydrolysis

[0063] metal and element alkoxides of Ti, Zr, Sn, Si, B, Al

[0064] metal and element acetylacetonates Ti(acac)₄, Zr(acac)₄

[0065] mixed compounds of metal/element alkoxides and metal acetylacetonates

[0066] Ti(acac)₂(OiPR)₂

[0067] organic amino compounds of Ti, Zr, Sn, Si, B, Al

[0068] element oxides

[0069] metal oxides

[0070] element hydroxides

[0071] metal hydroxides

[0072] water-containing oxides

[0073] water-containing phosphates

[0074] water holding ability

[0075] proton conductivity

[0076] polysulfone Udel®

[0077] polyether ether ketone Victrex®

[0078] polymeric acid halides

[0079] cation exchange polymers

[0080] cation exchange polymer membranes

[0081] polymer proton conductor

[0082] proton self conductivity

[0083] membrane fuel cells

[0084] H₂ fuel cells

[0085] direct methanol fuel cells

[0086] membranes

[0087] membrane process

[0088] application temperature >80° C.

[0089] thermal stability 

1. Membranes containing at least one polymeric acid halide, characterized in that before, during or after the membrane formation process salts, metal oxides or metal hydroxides or their organic precursors are incorporated into the membrane.
 2. Membranes according to claim 1 characterized in that the polymeric acid halide is an aryl main chain polymer and carries SO₂X, POX₂, COX or BX₂ groups (X═F, Cl, Br, I) and is chosen from the group of polyether sulfones, polysulfones, polyphenyl sulfones, polyether ether sulfones, polyether ketones, polyether ether ketones, polyphenylene ethers, polydiphenylphenylene ethers, polyphenylene sulfides or is a copolymer, that contains at least one of these components.
 3. Membranes according to one or more of claims 1 to 2, characterized in that they contain a salt, element or metal oxide or metal hydroxide, which has been obtained by hydrolysis and/or sol/gel reaction before, during or after membrane formation and is chosen from the following precursors: metal/element alkoxides/esters of Ti, Zr, Sn, Si, B, Al metal acetylacetonates, e.g. Ti(acac)₄, Zr(acac)₄ mixed compounds of metal/elemental alkoxides and metal acetylacetonates, e.g. Ti(acac)₂(OiPr)₂ etc. organic amino compounds of Ti, Zr, Sn, Si, B, Al
 4. Membranes according to claim 3, characterized in that the SO₂X, POX₂, COX or BX₂ groups (X═F, Cl, Br, I) of the membrane polymer are changed by a hydrolysis reaction which happens after membrane formation to SO₃Y, PO₃Y₂, COOY or B(OY)₂ groups (Y═H, a univalent or bivalent metal cation, ammonium ion, imidazolium ion, pyrazolium ion, pyridinium ion).
 5. Membranes according to one or more of claims 1 to 4 characterized in that they are additionally covalently cross-linked.
 6. Membranes according to one or more of claims 1 to 5 characterized in that the membranes are posttreated with phosphoric acid to generate in the membrane matrix from the metal oxides and/or metal hydroxides and/or metal oxides hydroxides the metal phosphates or element phosphates or metal hydrogenphosphates or element hydrogenphosphates or metal dihydrogenphosphates or element dihydrogenphosphates, which contribute to proton conductivity.
 7. Process for the preparation of membranes according to one or more of claims 1 to 6 characterized in that the following components are mixed in a dipolar-aprotic solvent such as N-methylpyrrolidinone (NWP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) or sulfolane or in an ether solvent such as tetrahydrofuran, dioxan, glyme, diglyme, triglyme etc.: a polymeric acid halide with SO₂X, POX₂, COX or BX₂ groups (X═F, Cl, Br, I), and at least metal-organic or element organic compounds according to the compounds of claim
 3. 8. Process according to claim 7 characterized in that the polymer solution of claim 6 is cast into thin films on a support (glass-plate or metal plate, tissue, wovens or non-wovens, fleece, porous (polymer)membrane), the solvent is evaporated at temperature of 80 to 150° C. at normal pressure or under vacuum and the formed thin film is posttreated as follows, whereby the order of posttreatment steps can vary and also optionally the steps (1) and/or (2) and/or (3) can be omitted: (1) in water at T=50 to 100° C. (2) in 1 to 100% mineral acid (hydrohalic acid, sulfuric acid, phosphoric acid) at T=50 to 100° C. (3) in 1 to 50% aqueous base (e.g. ammonia solution, amine solution, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, calcium hydroxide solution, barium hydroxide solution) or in an anhydrous liquid amine or mixture of different amines. (4) in water at T=50 to 100° C.
 9. Use of membranes according to claim 1 to produce energy by an electrochemical way.
 10. Use of membranes according to claim 1 to produce energy or substances by a photochemical way.
 11. Use of membranes according to claim 1 as component in membrane fuel cells (H₂ or direct methanol fuel cells) at temperatures of from 0 to 180° C.
 12. Use of membranes according to claim 1 electrochemical cells.
 13. Use of membranes according to claim 1 in secondary batteries.
 14. Use of membranes according to claim 1 in electrolysis cells.
 15. Use of membranes according to claim 1 in membrane separation processes such as gas separation, pervaporation, perstraction, reverse osmosis, electrodialysis and diffusion dialysis. 